Crystal structures of 1,1′-di(methylacetato)- and 1,1′-di(chloroethoxyethyl)-2,2′-biimidazole

1,1′-Di(methylacetato)-2,2′-biimidazole, C₁₂H₁₄N₄O₄, crystallizes from methanol in the space groupP2 ₁/c, wherea=9.535(2),b=13.385(2),c=5.1208(8) Å,V=652.2(2) ų, andZ=4.1,1′-Di(chloroethoxyethyl)-2,2′-biimidazole, C₁₄H₂₀Cl₂N₄O₂, crystallizes from cyclohexane in the space groupPbca, wherea=12.372(2),b=8.959(2),c=14.840(2) Å,V=1644.9(5) ų, andZ=8. The structures were refined toR=0.041 (1380 observed reflections) andR=0.043 (3243 observed reflections), respectively. Both molecules crystallize with coplanar rings and the substituents assume atrans configuration with a center of inversion between the bridging carbon atoms.     

Structure of 2-acetoxy-1,2-di(1-adamantyl)ethanone

The structure of 2-acetoxy-1,2-di(1-adamantyl)ethanone is reported. The steric requirements of the two adamantyl groups affect the structure in three ways—a slight elongation of the central bond, a small expansion of the angles about the central bond, and a conformation in which the C(sp²)-connected adamantyl group virtually bisects the large substituents attached to the sp³ carbon.     

Synthesis and X-ray crystal structure of a complex formed by reaction of 1,2-bis(2′-pyridylethynyl)benzene and mercury(II) chloride

The X-ray crystal structure of the complex formed between 1,2-bis(2′-pyridylethynyl) benzene and mercuric(II) chloride is described. The complex (C₄₀H₂₄Cl₆Hg₃N₄) crystallized in the triclinic space group P-1 with a=9.0414(6), b=9.4631(7), c=12.1134(9) ?, α=97.4680(10), β=94.8130(10), γ=105.4700(10)°. The structure reveals that the ligand is distorted from planarity to accommodate the mercury cation and a third mercuric chloride moiety is held between two ligand-mercury coordination complexes. The central mercury cation has octahedral coordination geometry surrounded by six chlorides while the other two mercury cations have distorted tetrahedral geometry each coordinated by two pyridyl nitrogen atoms and two chlorides.     

Crystal structures of 1,1-di(p-substituted phenyl)-2,2-dinitroethylenes

The X-ray crystal structures of 1,1-di(p-methylphenyl)-2,2-dinitroethylene (2), 1,1-di(p-methoxylphenyl)-2,2-dinitroethylene (3), 1,1-di(p-fluorophenyl)-2,2- dinitroethylene (4), 1,1-di(p-chlorophenyl)-2,2-dinitroethylene (5), and 1-phenyl-1- (p-nitrophenyl)-2,2-dinitroethylene (6) are reported and compared with that of 1,1-diphenyl-2,2-dinitroethylene (1). Owing to steric repulsion between the aryl rings, the single bond lengths between C(1) and the two ring carbons atoms are longer than the normal sp²–sp² bond distance of 1.46 Å. For 4–6 in which the aryl rings contain electron-withdrawing substituents (F, Cl, NO₂), the double bonds between C(1) and C(2) are shorter than those in 2 and 3, whose aryl rings containing electron-donating substituents. Furthermore, the steric repulsion between the aryl rings and C NO₂ fragments results in an appreciable twist about the central double bond. The two aryl rings of compounds 1–6 make dihedral angles of 77.7, 66.6, 62.8, 80.9, 82.0, and 71.2°, and the two C NO₂ fragments make dihedral angles of 68.5, 67.8, 65.9, 76.9, 73.0, and 71.9°, respectively.     

Synthesis and crystal structure of 3,5-di(2-propenyl)-6-phenyl-1,3,5-triazine-2,4-dione and 2-dimethylamino-4-ethoxycarbonylmethoxy-6-phenyl-1,3,5-triazine

The title compound 3,5-di(2-propenyl)-6-phenyl-1,3,5-triazine-2,4-dione has been synthesized by the reaction of 6-phenyl-1,3,5-triazine-2,4-dione with allyl bromide. Its structure was determined by X-ray single crystal diffraction. The crystal belongs to orthorhombic, space group Pbca with the following crystallographic parameters: a = 16.282(4) Å, b = 8.888(2) Å, c = 19.281(5) Å, = 90°, = 90°, = 90°, = 0.088 mm^–1, V = 2790.1(13) ų, z = 8, Dx = 1.282 mg/m³, F(000) = 1136, T = 293(2) K, 2.11° 25.02°, the final R factor: R ₁ = 0.0430, wR₂ = 0.0981. The X-ray results demonstrate that the reaction of 6-phenyl-1,3,5-triazine-2,4-dione with allyl bromide in the presence of N,N-dimethylformamide and potassium carbonate yields the N-alkylated product. The title compound 2-dimethylamino-4-ethoxycarbonylmethoxy-6-phenyl-1,3,5-triazine has been synthesized by a new reaction, in which the solvent N,N-dimethylformamide involves. Its structure was determined by X-ray single crystal diffraction. The crystal belongs to triclinic, space group P-1 with the following crystallographic parameters: a = 7.977(2) Å, b = 10.394(3) Å, c = 10.837(3) Å, = 111.774(5)°, = 104.050(5)°, = 99.446(5)°, = 0.093 mm^–1, V = 776.6(4) ų, z = 2, Dx = 1.293 mg/m³, F(000) = 320, T = 293(2) K, 2.14° 25.03°, the final R factor: R ₁ = 0.0582, wR ₂ = 0.1399. The distance of N(4) C(2) (1.339 Å) is much shorter than the length of normal C N (1.47 Å) and very close to that of C-N (1.33 Å), which is indicative of the significant double bond character.     

Synthesis and crystal structure of cobalt(III) complex with a Schiff base and azide

The cobalt(III) complex, [Co(L)₂(N₃)₂]₂(ClO₄)₂, L being a Schiff base N-[phenyl(pyridin-2-yl)methylene]aniline has been synthesized and the crystal structure determined using X-ray crystallography. The complex crystallizes in triclinic system, space group P-1 with unit cell parameters a=10.9367(9) ?, b=18.0817(17) ?, c=20.1629(16) ?, α=111.341(2)°, β=91.622(2)°, γ=107.5030(10)°, V=3499.1(5) ?³ and Z=2. It crystallizes with two independent molecules in the asymmetric unit. The two cobalt atoms are hexa-coordinate and have a distorted octahedral geometry, satisfied by four nitrogen atoms from two molecules of the Schiff base and two nitrogen atoms from the monodentate azide group. The perchlorate ions are non-coordinating.     

Synthesis and crystal structure of a copper coordination polymer [(Cu(btapo)2BrCH3OH)+Br−]n (btapo=1,3-bis(benzotriazol-1-yl) propan-2-ol)

A new coordination polymer [(Cu(btapo)₂BrCH₃OH)⁺Br⁻]_n (btapo = 1,3-bis(benzotria- zol-1-yl) propan-2-ol) was synthesized by the reaction of CuBr₂ and btapo, a new ligand synthesized in our laboratory, in THF. Its structure was determined by single-crystal X-ray crystallography. It crystallizes in tetragonal I4(1)/a space group with the crystal cell parameters of a=11.987(9) ?, c=54.24(4) ?, V=7794(10) ?³, and Z=8. The crystal X-ray analysis shows that each copper atom is five-coordinated with a bromine atom and four nitrogen atoms from four ligands to form a slightly distorted square pyramid. Each ligand bridges two copper atoms to form a two-strand helical chain. The chains are further extended to a three-dimensional network by the hydrogen bonds between the hydroxyl groups and the bromine anions. Supplementary material Crystallographic data for the structure reported in this paper have been deposited with the Cambridge Crystallographic Data Center as supplementary publication no. CCDC 600471. Copies of the data can be obtained free of charge on application to CCDC, 12 Union Road, Cambridge CB2 1EZ, UK (Fax;(+44) 1223–336-033; e-mail: deposit@ccdc.cam.ac.uk).     

5-溴-2-(4-甲基哌啶-1-基)嘧啶的晶体结构及密度泛函理论研究

嘧啶类衍生物在医药、化工和功能材料等领域有着重要应用。在药物研发,特别是抗癌药物研发领域中,5-溴-2-(4-甲基哌啶-1-基)嘧啶是一种含嘧啶环的重要中间体。本文通过一步芳香亲核取代反应合成了5-溴-2-(4-甲基哌啶-1-基)嘧啶,经溶液结晶法获得其单晶体,并进行了晶体学分析(晶系:正交晶系,空间群:P2₁2₁2₁,晶胞:a=10.181 42(6) nm, b=17.620 0(8) nm, c=10.179 02(5) nm,Z=4,ρ_c＝1.478 g·cm^-3,R=0.056 6,wR=0.168 8)。标题化合物的最优结构和前线轨道能量在B3LYP/6-311G(d, p)模式下使用密度泛函理论(DFT)计算得到,经DFT优化的结果与实验确定的数据相近。此外,为进一步揭示标题化合物的物理化学性质,通过DFT进一步研究了分子的静电式和前线分子轨道。     

Crystal and molecular structure of 6,7-benzo-3,4 (1,4-dimethoxy-2,3-naphtho)-1,5-dioxosuberane

The crystal and molecular structure of the title compound (2) C₂₁H₁₆O₄ has been determined by an X-ray analysis, by direct methods from diffractometer data and refined by full-matrix least squares. The compound (2) crystallizes in the space group P2₁/a, with cell parameters:a=36.432(5),b=5.512(3),c=8.269(5) Å, =108.0(3)°,z=4,D _c =1.397 g/cm^–3,R=7.8 for 1136 observed reflections. The conformation of the tetracyclic ring system shows a folding of two planar parts of the carbon skeleton about an axis passing thorough C8 and C16 of the seven membered ring C.     

Synthesis and Crystal Structure of 3-[(Naphthalen-2-yl)methyl]Isocoumarin

Abstract 3-[(Naphthalen-2-yl) methyl]isocoumarin was synthesized by the reaction of homophthalic acid with 2-(naphthalen-2-yl)acetyl chloride at elevated temperature and its crystal structure has been determined (C₂₀H₁₄O₂), Mr = 286.31, a = 13.704(3), b = 7.356(4), c = 7.042(7) ?, β = 99.21(3)°, space group Pc, Z = 2, and V = 700.7(8) ?³. The isocoumarin and the naphthalene ring systems are individually planar and the dihedral angle between the mean planes of these two ring systems is 70.05(8)°. Graphical Abstract Synthesis and crystal structure of 3-[(Naphthalen-2-yl)methyl]isocoumarin Aamer Saeed, Junmei Liang, Masood Parvez The synthesis and crystal structure of a novel isocoumarin, 3-[(naphthalen-2-yl)methyl]isocoumarin has been presented.      

Synthesis and molecular structure of 4,4,5,5-tetramethyl-2-(1-(phenylsulfonyl)propan-2-yl)-1,3,2-dioxaborolane

The compound 4,4,5,5-tetramethyl-2-(1-(phenylsulfonyl)propan-2-yl)-1,3,2-dioxabo- rolane has been prepared by the rhodium catalyzed hydroboration of allyl phenyl sulfone and characterized by a single crystal X-ray diffraction study. The title compound crystallized in the monoclinic space group P2₁/c, with cell parameters a=16.0728(8) ?, b=9.8884(5) ?, and c=10.1926(5) ?, β=92.067(1)°, Z=4, and V=1618.90(14) ?³. The structure was solved by direct methods and refined to a final R=0.0449 for 3627 reflections with I>2σ(I). No significant intramolecular or intermolecular interaction is observed with the Lewis acidic boron atom.     

The Synthesis and Structure of Two Novel <Emphasis Type="Italic">N</Emphasis>-(Benzothiazol-2-yl)benzamides

Abstract  Two novel benzothiazoles 2-chloro-N-(benzothiazol-2-yl)benzamide (1) and 2-chloro-N-(6-cyanobenzothiazol-2-yl)benzamide (2) were obtained in multistep synthesis. They were characterised by means of IR, ¹H- and ¹³C-NMR spectroscopy and also by single-crystal X-ray diffraction. The compound 1 crystallises with triclinic space group P , a = 9.5923(8) ?, b = 9.8583(8) ?, c = 13.8962(10) ?, α = 89.162(6)°, β = 77.741(7)°, γ = 80.064(7)°, V = 1264.5(2) ?³, Z = 4 and compound 2 crystallises as methanol solvate with monoclinic space group P 2₁/n, a = 7.5093(9) ?, b = 13.0211(14) ?, c = 16.032(2) ?, β = 92.717(10)°, V = 1565.9(3) ?³, Z = 4. Both crystal structures consist of discrete dimers connected into a three-dimensional network by intermolecular C–H···O and C–H···X (X = Cl or S) hydrogen bonds and by face-to-face π–π stacking interactions. Index Abstract  The synthesis and structure of two novel N-(benzothiazol-2-yl)benzamides. Irena Ćaleta, Dominik Cinčić, GraceKarminski-Zamola and Branko Kaitner. Hydrogen bonds and π–π interactions in N-(benzothiazol-2-yl)benzamides N-(benzothiazol-2-yl)benzamides.      

Redetermination of the structure of bis[chloro-2-(2-hydroxy-4,5-dimethylphenylazo)-5,5-dimethyl-4,5,6,7-tetrahydrobenzothiazol-7-on] copper(II) complex

The crystal structure of C₁₇H₁₈ClCuN₃O₂S (M = 854.78, monoclinic, P2₁/c, a = 8.316(2), b = 18.461(4), c = 11.774(2) Å, = 99.64(3)°, V = 1782.0(7) ų, Z = 4) is formed by dimeric molecules [C₁₇H₁₈ClCuN₃O₂S]₂ with two monomeric units linked together by two chlorine atoms. The Cu atom is coordinated by two chlorine atoms, an oxygen atom, the azo nitrogen atom attached to the benzene ring, and the nitrogen atom of the thiazole ring, in the form of a distorted tetragonal pyramid.     

以2-甲基-丙烯酸,4-(吡啶-4-偶氮)-苯酯为配体的四个配位化合物的合成、晶体结构和紫外吸收

4个单核配位化合物,[Zn(Maape)2(H2O)2(NO3)2] (1, 单核), [Cu(Maape)2(H2O)2(NO3)2] (2, 单核), [Zn(Maape)2Cl2] (3, 单核), [Zn(Maape)(H2O)4SO4] (4, 单核),都是用过渡金属盐和配体2-甲基-丙烯酸,4-(吡啶-4-偶氮)-苯酯合成的.四个化合物由单晶X-射线衍射和结构分析表明都是单核化合物.另外,还通过红外和元素分析对其进行表征.配位化合物的结构不仅受配位金属离子的影响还受不同配位阴离子的影响.化合物1和2的结构都是由一个金属离子中心、2个配位硝酸根离子和2个配体分子组成的单核配合物.化合物3的单核结构中包含一个Zn(II)、2个氯离子和2个配体分子.而化合物4的不对称单元[Zn(Maape)(H2O)4SO4]中Zn(II)中心位于二重对称轴上.在本文中,配体和4个化合物都在323 nm处有最高紫外吸收峰.     

Reaction of 1,2-bis(2,6-dicarboxypyridin-4-yl)ethyne and imidazole with Cu(II) generates a discrete complex not a coordination polymer: crystal structure of [μ-4,4′-(1,2-ethynediyl)-bis(pyridine-2,6-dicarboxylato)-N,O, O′-μ-N′, O′′, O′′′]-diaqua-bis(imidazole)-dicopper(II)

Reaction of 1,2-bis(2,6-dicarboxypyridin-4-yl)ethyne and imidazole with Cu(II) produces crystals containing a discrete complex of [μ-4,4′-(1,2-ethynediyl)-bis(pyridine-2,6-dicarboxylato)-N, O, O′-μ-N′, O′′, O′′′]-diaqua-bis(imidazole)-dicopper(II) complex (1), [(C₁₆H₄N₂O₈)(C₃H₄N₂)₂(H₂O)₂Cu₂] instead of a linear coordination polymer. The complex crystallizes in the monoclinic space group P2₁/n with a = 5.3763(8) ?, b = 18.522(3) ?, c = 11.4827(7) ?, β = 93.705(3) ° and Z = 2. The complex sits on a center of symmetry such that the two halves of the molecule are related by inversion symmetry. The molecules pack in layers in which the molecules are joined by intermolecular N–H⋯O hydrogen bonds between imidazole and carboxylate groups and O–H⋯O hydrogen bonds between carboxylate groups and water.     

Crystal Structures of (2-oxo-2H-Quinaxalin-1-yl)-acetic Acid and its Cobalt and Nickel Complexes and Their Comparison with (1,3-Dioxo-1,3-dihydro-isoindol-2-yl)-acetic Acid

Abstract The crystal structures of (2-oxo-2H-quinaxalin-1-yl)-acetic acid and its cobalt and nickel complexes are determined. The (2-oxo-2H-quinaxalin-1-yl)-acetic acid (1) crystallizes in orthorhombic, Pbca, a = 12.8571(11) ?, b = 9.4267(8) ?, c = 15.0095(13) ?, the cobalt complex of (2-oxo-2H-quinaxalin-1-yl)-acetic acid (2) crystallizes as dihydrate in triclinic, P-1 space group with a = 4.81150(10) ?, b = 11.8631(2) ?, c = 12.4867(3) ?, α = 71.7800(10)°, β = 79.2490(10)°, γ = 84.9020(10)° whereas the nickel complex of (2-oxo-2H-quinaxalin-1-yl)-acetic acid (3) crystallizes in monoclinic, P2₁/c space group with a = 14.9210(5) ?, b = 4.81730(10) ?, c = 15.7672(5) ?. and β = 99.823(2)°. The crystal structure of the ligand and the complexes are compared with structures of (1,3-dioxo-1,3-dihydro-isoindol-2-yl)-acetic acid and its cobalt and nickel complexes. Index Abstract The crystal structures of (2-oxo-2H-quinaxalin-1-yl)-acetic acid and its nickel and cobalt complexes are compared with (1,3-dioxo-1,3-dihydro-isoindol-2-yl)-acetic acid and its corresponding complexes with nickel(II) and cobalt(II).      

Synthesis and crystal structure of 3-chloro-<Emphasis Type="Italic">N</Emphasis>-(2-chloro-5-(1,3-dioxo-4,5,6,7-tetrahydro-1H-isoindol-2(3H)-yl)-4-fluorophenyl)-2,2-dimethylpropanamide

The title compound 3-chloro-N-(2-chloro-5-(1,3-dioxo-4,5,6,7-tetrahydro-1H-isoindol-2(3H)-yl)-4-fluorophenyl)-2,2-dimethylpropanamide was synthesized by the reaction of 2-(5-amino-4-chloro-2-fluorophenyl)-4,5,6,7-tetrahydro-2H-isoindole-1,3-dione with 3-chloro-2,2-dimethylpropanoyl chloride. Its structure was determined by X-ray single crystal diffraction. The crystal belongs to triclinic, space group P-1 with the following crystallographic parameters: a = 9.595(3) Å, b = 12.093(4) Å, c = 18.433(6) Å, α = 83.961(5)^∘, β = 84.819(5)^∘, γ = 67.920(5)^∘, μ = 0.361 mm⁻¹, V = 1967.9(10) ų, Z = 4, Dx = 1.395 mg/m³, F(000) = 856, T = 293(2) K, 1.11^∘ ≤ θ ≤ 25.01^∘. The X-ray results demonstrated that the reaction of 2-(5-amino-4-chloro-2-fluorophenyl)-4,5,6,7-tetrahydro-2H-isoindole-1,3-dione with 3-chloro-2,2-dimethylpropanoyl chloride in tetrahydrofuran at room temperature yielded 3-chloro-N-(2-chloro-5-(1,3-dioxo-4,5,6,7-tetrahydro-1H-isoindol-2(3H)-yl)-4-fluorophenyl)-,2-dimethylpropanamide.     

A structural study of copper(II) carboxylates: Crystal structure and physical characterisation of [Cu2(2-bromopropanoato)4(caffeine)2]

Based on the bond-valence sum model the continual transition between the bidentate and monodentate bonding mode of carboxylato group and minimum of Cu–O bond lengths were estimated. The dependence of Cu⋯Cu separation on Cu–N bond length in binuclear Cu(II) carboxylates with caffeine were derived and fitted to the observed data. The crystal structure of [Cu₂(2-bromopropanoato)₄(caffeine)₂] has been determined by X-ray crystallography. The structure consists of centrosymmetric binuclear units where the two Cu atoms are coordinated by four disordered bridging 2-bromopropionates and two caffeine ligands at the apices of a bicapped square prism. Both 2-bromopropionates show disorder of their –Br and –CH₃ substituents. Stacking π·π interactions between the adjacent caffeine molecules link the complex units in 1-D networks. The binuclear structure of the studied compound is consistent with magnetic data and EPR spectrum.     

New sulfur derivatives of 2,3-dichloropyrrolo[1,2-a] benzimidazol-1-one. Demonstration of regioselective thiolate addition and X-ray diffraction structures of 2-chloro-3-methylthiopyrrolo[1,2-a]benzimidazol-1-one and 2,3-di(benzylthio)pyrrolo[1,2-a]benzimidazol-1-one

The reaction of thiols with the heterocyclic compound 2,3-dichloropyrrolo[1,2-a] benzimidazol-1-one (1) has been investigated as a route to new redox-active, bidentate sulfur ligands. Treatment of 1 with either methylthiol or benzylthiol in the presence of pyridine affords monosulfide compounds 2-chloro-3-methylthiopyrrolo[1,2-a] benzimidazol-1-one (2) and 2-chloro-3-benzylthiopyrrolo[1,2-a]benzimidazol-1-one (3) and the disulfide derivatives 2,3-di(methylthio)pyrrolo[1,2-a]benzimidazol-1-one (4) and 2,3-di(benzylthio)pyrrolo[1,2-a]benzimidazol-1-one (5). The substitution of the first chlorine group in 2,3-dichloropyrrolo[1,2-a]benzimidazol-1-one (1) occurs regioselectively at C-3 to produce 2-chloro-3-methylthiopyrrolo[1,2-a]benzimidazol-1-one (2) and 2-chloro-3-benzylthiopyrrolo[1,2-a]benzimidazol-1-one (3), followed by replacement of the remaining chlorine group to furnish the disulfide compounds 4 and 5. The new thiols have been isolated by column chromatography and characterized in solution by spectroscopic methods. The molecular structures of 2-chloro-3-methylthiopyrrolo[1,2-a]benzimidazol-1-one and 2,3-di(benzylthio)pyrrolo[1,2-a]benzimidazol-1-one have been determined by X-ray crystallography. Compound 2 crystallizes as two independent molecules in the monoclinic space group P2₁/c, a = 13.221(2) Å, b = 18.478(2) Å, c = 8.948(1) Å, = 100.088(3)°, V = 2152.3(5) ų, Z = 8, and d_calc = 1.547 Mg/m³; R = 0.0354, R_w = 0.0739 for 2820 reflections with I > 2(I). Compound 5 crystallizes in the triclinic space group P-1, a = 5.180(1) Å, b = 11.494(2) Å, c = 17.243(3) Å, = 86.024(3)°, = 88.606(4)°, = 81.235(3)°, V = 1012.1(4) ų, Z = 2, and d_calc = 1.360 Mg/m³; R = 0.0354, R_w = 0.0692 for 2655 reflections with I > 2(I). The redox properties of the disulfide compounds 4 and 5 have been explored by cyclic voltammetry, where a one-electron reduction at ca. –1.10 V has been observed for each compound. The site of electron accession in has been established by carrying out molecular orbital calculations at the extended Hüuckel level on the model compound 2,3-di(thio)pyrrolo[1,2-a]benzimidazol-1-one.     

Crystal and molecular structure of trans-bis(dodecylamine) bis(dimethylglyoximato)cobalt(III) nitrite

An octahedral geometry for the molecule of the title complex with very slight distortions around Co(III) is confirmed by single-crystal X-ray diffraction study. The molecular structure of the complex has been shown to contain two dodecylamine moieties in the trans orientations, two N-bonded dimethylglyoximato (DMG) groups and an uncoordinated nitrite ion.